JPS6076509A - Manufacture of elastomer chlorosulfonated ethylene polymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for the modification of ethylene i coalescein, specifically a granular material having a density of about α87 to about α93 g'/CC and a pore volume of about α1 to about 1 CC/gL. of ethylene polymer is reacted with a gaseous chlorosulfonating agent in the absence of a solvent or diluent to form a particulate elastomerol sulfonate having a tensile modulus of less than or equal to about zooopsi and a crystallinity of less than or equal to about 10%. This type of modification method for producing polymers is concerned. The elastomeric polymers thus produced can be cured into crosslinked products useful in the manufacture of film materials such as extrusion coatings around wires and cables and base polymers for flame retardant compositions.

BACKGROUND OF THE INVENTION Elastomeric chlorosulfonated ethylene polymers are commercially attractive because they possess a number of desirable properties. Desirable properties include (a) chemical solvent resistance;
(b) Ozone resistance, (c) Abrasion resistance, (d) Outdoor weather resistance, (@) Excellent operating temperature, i.e. flexibility over a temperature range of approximately -20°C to approximately 120°C. Examples include having. Accordingly, cured chlorosulfonated ethylene polymers with the above-mentioned properties and compositions based on the polymers can be used in film materials such as extrusion coatings on wire and cable loops or as base polymers in flame retardant compositions. It has applications in a variety of fields including the production of

Traditionally, the production of chlorosulfonated ethylene polymers has been carried out by a solution method in which the polymer is reacted with a chlorosulfonating agent in a solvent. The so-called solution process generally requires the solvent to be removed from the chlorosulfonated polymer upon completion of the reaction U3 by heating the reaction system to a temperature high enough to evaporate the solvent. However, at the temperatures employed for solvent removal, chlorosulfonated polymers tend to aggregate and become difficult to handle and process.

It has also been proposed to chlorosulfonate ethylene polymers by a process that involves reacting the polymer with a gaseous polytetrasulfonating agent. This process did not appear to be particularly successful because the ethylene polymer was heterogeneously p-sulfonated. As pointed out in US Pat. No. 1,547,855, cured products obtained from this type of polysulfonated ethylene polymer had poor properties.

The detailed description of the invention enables the chlorosulfonation of diethylene polymers in a manner that avoids the use of solvents and diluents and the attendant disadvantages, and is demonstrated by its excellent and balanced properties. As shown in this book, a homogeneously chlorosulfonated granular elastomeric ethylene 'rt Spring Break is published by S.H. Additionally, the chlorosulfonated ethylene polymers of the present invention are easy to handle and process due to their particulate nature. Density of about α934r:/cc, preferably about 0.89 to about 091 bait/cc and density of about α1 to about I CC/g', usually about α1 to
about o, scc/gt, preferably about 0.2 to about 0.4
A particulate ethylene polymer having a pore volume of CC/anal is reacted with a gaseous chlorosulfonating agent to produce a pore volume of about 2.0009!11
This is achieved by producing a particulate elastomerol sulfonated polymer having a tensile modulus of less than or equal to about 10% and a crystallinity of less than about 10%.

The chlorosulfonated ethylene polymers thus produced are homogeneously chlorosulfonated and "elastomeric" and are comparable to commercially available solution-produced chlorosulfonated ethylene polymers. It has excellent balanced properties.

Ethylene polymers suitable for the purposes of the present invention having the densities and pore volumes described above are disclosed in U.S. Pat. Ethylene-03~C$ alpha olefins obtained by reacting ethylene with at least one alpha monoolefin under low pressure as described in U.S. Patent Application No. 4BO, 296 filed on 29 It is a polymer.

Particularly desirable ethylene polymers for purposes of the present invention have the densities and pore volumes described above and have about 50 to about 99, preferably about 75 to about 96, mole percent ethylene and about 1 to about 5 mole percent ethylene.
0, preferably from about 4 to about 25 mol % of at least one Cs to Cs alpha monooletuin, such as globilene,
butene-1, pentene-1,4-methylpentene-1,
Includes such as hexene-1, heptene-1 and octene-1.

More desirable ethylene polymers to be chlorosulfonated in accordance with the present invention have an average particle size of about 200 to about 1 soo, preferably from about 300 to about 1,000 chloro, from about 10 to about 30, preferably from about 15 to about a bulk density of 24, a pore volume of about α1 to about 1, usually about 01 to about 0.5, preferably about 0.2 to about α4 cc/gr, and a pore volume of about 0.87 to about α93, preferably about 0.89 to about α9M
It has a density of gr,/cc.

Upon treatment with a gaseous chlorosulfonating agent, JJ has a tensile modulus of less than about 2,000 psi and a crystallinity of less than about 10%, preferably from 0 to about 5%, and from about 5 to about 5%. About 55% heavy, preferably about 15% to about 40% dark
total chlorine content and about 01 to #10ffiffi%,
Preferably, the time is sufficient to obtain a chlorosulfonated ethylene polymer having a sulfur content of about 0.5 to about 5 m ffi %.

CI of hydrogen atoms on the main chain of this treated L1 ethylene polymer
It is thought that this causes IU exchange by so, cx s and so.

The actual time of processing generally ranges from about 20 to about 10 hours depending on the particular ethylene polymer being chlorosulfonated, the chlorsulfonating agent being used, and the temperature and pressure employed. It changes.

Generally, suitable temperatures range from about 50°C to about 150°C;
Preferably, the temperature is in the range of about 0°C to about 100°C. The pressure at which the reaction is carried out can vary from atmospheric pressure to about 1,000 psi. Ta! provided that neither the reactants nor the by-products condense under the reaction conditions employed. Generally, the higher the temperature and pressure, the shorter the reaction time.

Chlorsulfonating agent used in carrying out the reaction,
For example, the amount of sulfuryl chloride or a mixture of sulfur dioxide and chlorine may range from about 10 to about 200% by volume, preferably from about 20% to about 200% by weight, based on the loading of the ethylene polymer being treated.
It is approximately 100% by weight. SO as reactant or modifier
In an example using a mixture of 3 and C12, C1t vs.
The molar ratio of O1 is about 5:1 to 1021, preferably about 5=
It is 1.

If desired, an inert gas such as nitrogen can be used in conjunction with the gaseous modifier as a fluidizing agent, diffusion aid, and heat dissipation.

The properties described herein were measured using the test methods described below.

I adjusted it so that Then, the density gradient Density measurements were carried out at the tower.

The 1' calculation from the analytical data was based on the mold fraction retained on the screen.

Bulk Density: Pour the polymer to 1 oast through a 378 diameter funnel into a 100 mm graduated tube without shaking. High density was determined based on the difference in density between unfilled horizontal tubes and filled filled tubes.

Crystallinity duFont-99 with pressure DSC cell
0'$). , □ Engineering, 1 Ka. -1°8C).

Compression molding and 1% 111 wire modulus of 8TM-
Measured using D-638.

638 was tested.

The film produced was tested according to ASTM-D-638.

EXAMPLES The following examples are set forth to illustrate the invention and are not intended to limit the invention.

Unless otherwise indicated, the ethylene polymers used as starting materials in the examples were prepared by the method described in U.S. Patent Application No. 480.296, filed March 29, 1983. Ta.

2 liter glass-backed stainless steel or Hastelloy with thermocouple and motor actuated U-shaped Hastelloy stirrer 55% Nickle, 17% Molybdenum, 1 Chromium
6% iron, 6% tungsten and 4% tungsten) The polyethylene polymer is then sulfonated in a reactor.

A Hesteroy dip tube (2 cIR diameter) was used to feed the gaseous modifier into the reactor. Unreacted modifier and HCI were vented to a collection trap containing a 25% NaOH water bath. The gaseous modifier is about 15 to about 450 ps
It was supplied at a rate of 8-15 gr/hr for C1, and at a rate of 2-3 gr/hr for SO7 under a pressure of i. About 200 to about 10,100 O of the polymer to be treated was placed in a reactor and heated with an external heater. No catalyst was used in carrying out these examples.

After adding the polymer to the reactor and heating to the desired reaction temperature,
The polymer was stirred with a stirrer and the gaseous modifier was fed. During the modification process, samples of the modified polymer were removed from the reactor and tested for sulfur and chlorine content and percent crystallinity. At the end of the reaction, the flow of gaseous modifier is stopped and unreacted SOf and/or CI,
The product was allowed to cool in the reactor while purging the reaction vessel with nitrogen to remove HCI byproducts.

Three types of granular low density ethylene-butene-1 copolymer A,
BSC was chlorosulfonated according to the invention. The polymer had the following properties.

BC Density gmAc α926 [1895α875 Mol% of butene-1 in copolymer 2.4 9.4 20 Crystallinity 1 50 24 13 Particle size (average) μ 400 500 400 Pore volume c
c/f-(130,,!16 (L37 bulk density 27
21 21 Pull M! Elastic modulus psl 45.300 8,800 1
,160 tensile strength p13 2J90 1,840
290 Elongation% 490 $155 920 Elongation of the engineered tyrene polymer at a temperature of 60°C to 100°C about 3 to 1
Dichlorosulfonation by reaction with a gaseous mixture of SO3 and CI for 0 hours produced a chlorosulfonated polymer with the properties listed in Table 1.

Polymer 'A is described in US patent rfS4.302.56540
FC was produced according to the disclosed aromatic fermentation.

Table 1 Chlorine% 50 15 12 27-55 Sulfur% 2.
4 12 H0,9-14 Crystallinity% 0 4.7 2.
7 < 2 tensile modulus psi 950 920 380 <500 tensile strength psl 590 820 '320 400-500 elongation % i, 925 680 890 hard E, 1. d
uPont® The data in this table shows that elastomers produced in accordance with the present invention have properties comparable to commercially available chlorosulfonated polymers.

To further illustrate the need for an ethylene polymer with the density and pore volume described above, a granular ethylene-butene-1 copolymer with a density of 0.935 gm/CC and a pore volume of approximately 0.3 CC7 gm was used. A control test was conducted.

This copolymer was chlorosulfonated in the manner described above in Example 1 using a mixture of gaseous sulfur dioxide and chlorine. Chlorsulfonation is performed at approximately 80°C to 100°C
It was carried out for a period of 8 hours at a temperature of . At the end of the 8 hour period, the chlorosulfonation product was analyzed and its properties determined.

Control 2 Chlorine% 20 Sulfur% 0.3 Crystallinity% 37 Tensile modulus: 3o, oo.

The chlorosulfonated polymer was not an elastomer product, as evidenced by its high tensile modulus and crystallinity.

Control 2 polymer was made according to the method disclosed in US Pat. No. 4,502,565.

The chlorosulfonated ethylene polymer of the present invention was developed in 1970.
U.S. Patent No. 4542.7, issued November 24, 2013
46 to form cross-linked products.

Procedural amendment (method) % formula % Display of the case Relationship with the case of the person who amended Patent Application No. 146165 of 1980 Name of the patent applicant Union Carbide Corporation Agent 〒103 Attachment of El of notice of amendment order 1988 October 50th = Nfu City, -1--1 hit the weight loss = Target of amendment Contents of amendment Correction of specification as attached (no change in content)

Claims (1)

Claims: (1) Reacting a particulate ethylene polymer having a density of about α87 to about 0.93 ann/cc and a pore volume of about 0.1 to about 1 cc/gr with a gaseous chlorosulfonating agent. let me,
A tensile modulus of less than about 2.000 pli and a tensile modulus of about 10
A process for the chlorsulfonation of ethylene polymers, characterized in that the process produces elastomeric, particulate chlorosulfonated ethylene polymers having a crystallinity of less than or equal to %. (2) The chlorsulfonation method according to claim 1, wherein the chlorsulfonation agent is gaseous sulfuryl chloride. (3) The chlorosulfonation method according to claim H, wherein the chlorosulfonation agent is a gaseous mixture of sulfur dioxide and chlorine. IAIjfln07~ftn0ILCr-/CI”/7
"lshi【hiniEL】;→-:?rfj6a1~about 0.5
A particulate ethylene-C3-C8 alpha olefin polymer having a pore volume of /cc is reacted with a gaseous chlorosulfonating agent to produce a tensile modulus of less than about 2.000 PII and a crystallinity of less than about 10%. 1. A method for chlorsulfonating an ethylene polymer, the method comprising: producing a particulate chlorosulfonated ethylene polymer having an elastomeric structure. (5) The polymer has a weight of about 0.89 to about 0.9/gr:
/ CC density and about a2 to about 0.4 CC/g
The chlorosulfonation method according to claim 4, having a pore volume of r. (6) The chlorosulfonation method according to claim 4, wherein the chlorosulfonating agent is gaseous sulfuryl chloride. (7) The chlorosulfonation method according to claim 4, wherein the chlorosulfonating agent is a gaseous mixture of sulfur dioxide and chlorine. (8) The polymer is a polymer of ethyl μ/ and butene-1! ! f. The chlorosulfonation method according to claim 4. (9) The chlorosulfonation method according to claim 4, which is carried out at a temperature of about 0°C to about 130°C. (10) The ethylene polymer has the following properties, namely about 20
The chlorine of claim 4 having an average particle size of 0 to about 1500, a bulk density of about 10 to about 30, a pore volume of about α1 to about 1, and a density of about 0.87 to about 0.93. Sulfonation method.